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At least 1,387 records · Page 77

Diagenesis Along Fractures in an Eolian Sandstone, Gale Crater, Mars

The Mars Science Laboratory rover Curiosity has been exploring sedimentary deposits in Gale crater since August 2012. The rover has traversed up section through approx.100 m of sedimentary rocks deposited in fluvial, deltaic, lacustrine, and eolian environments (Bradbury group and overlying Mount Sharp group). The Stimson formation lies unconformable over a lacustrine mudstone at the base of the Mount Sharp group and has been interpreted to be a cross-bedded sandstone of lithified eolian dunes. Mineralogy of the unaltered Stimson sandstone consists of plagioclase feldspar, pyroxenes, and magnetite with minor abundances of hematite, and Ca-sulfates (anhydrite, bassanite). Unaltered sandstone has a composition similar to the average Mars crustal composition. Alteration "halos" occur adjacent to fractures in the Stimson. Fluids passing through these fractures have altered the chemistry and mineralogy of the sandstone. Silicon and S enrichments and depletions in Al, Fe, Mg, Na, K, Ni and Mn suggest aqueous alteration in an open hydrologic system. Mineralogy of the altered Stimson is dominated by Ca-sulfates, Si-rich X-ray amorphous materials along with plagioclase feldspar, magnetite, and pyroxenes, but less abundant in the altered compared to the unaltered Stimson sandstone and lower pyroxene/plagioclase feldspar. The mineralogy and geochemistry of the altered sandstone suggest a complicated history with several (many?) episodes of aqueous alteration under a variety of environmental conditions (e.g., acidic, alkaline).

Ming, D. W.↗

Is Tridymite at Gale Crater Evidence for Silicic Volcanism on Mars?

The X-ray diffraction (XRD) instrument (CheMin) onboard the MSL rover Curiosity detected 17 wt% of the SiO2 polymorph tridymite (relative to bulk sample) for the Buckskin drill sample (73 wt% SiO2) obtained from sedimentary rock in the Murray formation at Gale Crater, Mars. Other detected crystalline materials are plagioclase, sanidine, cristobalite, cation-deficient magnetite, and anhydrite. XRD amorphous material constitutes approx. 60 wt% of bulk sample, and the position of its broad diffraction peak near approx. 26 deg. 2-theta is consistent with opal-A. Tridymite is a lowpressure, high-temperature mineral (approx. 870 to 1670 deg. C) whose XRD-identified occurrence on the Earth is usually associated with silicic (e.g., rhyolitic) volcanism. High SiO2 deposits have been detected at Gale crater by remote sensing from martian orbit and interpreted as opal-A on the basis H2O and Si-OH spectral features. Proposed opal-A formation pathways include precipitation of silica from lake waters and high-SiO2 residues of acid-sulfate leaching. Tridymite is nominally anhydrous and would not exhibit these spectral features. We have chemically and spectrally analyzed rhyolitic samples from New Mexico and Iwodake volcano (Japan). The glassy (by XRD) NM samples have H2O spectral features similar to opal-A. The Iwodake sample, which has been subjected to high-temperature acid sulfate leaching, also has H2O spectral features similar to opal-A. The Iwodake sample has approx. 98 wt% SiO2 and 1% wt% TiO2 (by XRF), tridymite (>80 wt.% of crystalline material without detectable quartz by XRD), and H2O and Si-OH spectral features. These results open the working hypothesis that the opal-A-like high-SiO2 deposits at Gale crater detected from martian orbit are products of alteration associated with silicic volcanism. The presence or absence of tridymite will depend on lava crystallization temperatures (NM) and post crystallization alteration temperatures (Iwodake).

Morris, Richard V.↗

Graphene Based Ultra-Capacitors for Safer, More Efficient Energy Storage

Current power storage methods must be continuously improved in order to keep up with the increasingly competitive electronics industry. This technological advancement is also essential for the continuation of deep space exploration. Today's energy storage industry relies heavily on the use of dangerous and corrosive chemicals such as lithium and phosphoric acid. These chemicals can prove hazardous to the user if the device is ruptured. Similarly they can damage the environment if they are disposed of improperly. A safer, more efficient alternative is needed across a wide range of NASA missions. One solution would a solid-state carbon based energy storage device. Carbon is a safer, less environmentally hazardous alternative to current energy storage materials. Using the amorphous carbon nanostructure, graphene, this idea of a safer portable energy is possible. Graphene was electrochemically produced in the lab and several coin cell devices were built this summer to create a working prototype of a solid-state graphene battery.

Composite battery↗

Mineralogy of Mudstone at Gale Crater, Mars: Evidence for Dynamic Lacustrine Environments

The Mars Science Laboratory Curiosity rover landed in Gale crater in August 2012 to assess the habitability of sedimentary deposits that show orbital evidence for diverse ancient aqueous environments. Gale crater contains a 5 km high mound of layered sedimentary rocks in its center, informally named Mount Sharp. The lowermost rocks of Mount Sharp contain minerals that are consistent with a dramatic climate change during Mars' early history. During the rover's traverse across the Gale crater plains to the base of Mount Sharp, Curiosity discovered sedimentary rocks consistent with a fluviolacustrine sequence. Curiosity studied ancient lacustrine deposits at Yellowknife Bay on the plains of Gale crater and continues to study ancient lacustrine deposits in the Murray formation, the lowermost unit of Mount Sharp. These investigations include drilling into the mudstone and delivering the sieved less than 150 micrometers fraction to the CheMin XRD/XRF instrument inside the rover. Rietveld refinement of XRD patterns measured by CheMin generates mineral abundances with a detection limit of 1-2 wt.% and refined unit-cell parameters of minerals present in abundances greater than approximately 5 wt.%. FULLPAT analyses of CheMin XRD patterns provide the abundance of X-ray amorphous materials and constrain the identity of these phases (e.g., opal-A vs. opal-CT). At the time of writing, CheMin has analyzed 14 samples, seven of which were drilled from lacustrine deposits. The mineralogy from CheMin, combined with in-situ geochemical measurements and sedimentological observations, suggest an evolution in the lake waters through time, including changes in pH and salinity and transitions between oxic and anoxic conditions. In addition to a geochemically dynamic lake environment, the igneous minerals discovered in the lake sediments indicate changes in source region through time, with input from mafic and silicic igneous sources. The Murray formation is predominantly comprised of lacustrine mudstone and is 150-200 m thick, suggesting long history of lake environments in Gale crater. Curiosity has traversed through the lowermost approximately 30 m of the Murray formation, and each additional sample provides clues about the climate on early Mars.

Rampe, E. B.↗

Molecular Dynamics Modeling of Carbon Nanotube Composite Fracture Using ReaxFF

Carbon nanotube (CNT) fiber reinforced composites with specific tensile strengths and moduli approaching those of aerospace grade carbon fiber composites have recently been reported. This achievement was enabled by the emerging availability of high N/tex yarns in kilometer-scale quantities. While the production of this yarn is an impressive advance, its strength is still much lower than that of the individual CNTs comprising the yarn. Closing this gap requires understanding load transfer between CNTs at the nanometer dimensional scale. This work uses reactive molecular dynamics simulations to gain an understanding at the nanometer scale of the key factors that determine CNT nanocomposite mechanical performance, and to place more realistic upper bounds on the target properties. While molecular dynamics simulations using conventional force fields can predict elastic properties, the ReaxFF reactive forcefield can also model fracture behavior because of its ability to accurately describe bond breaking and formation during a simulation. The upper and lower bounds of CNT composite properties are investigated by comparing systems composed of CNTs continuously connected across the periodic boundary with systems composed of finite length CNTs. These lengths, effectively infinite for the continuous tubes and an aspect ratio of 13 for the finite length case, result from practical limitations on the number of atoms that can be included in a simulation. Experimentally measured aspect ratios are typically on the order of 100,000, so the calculated results should represent upper and lower limits on experimental mechanical properties. Finally, the effect of various degrees of covalent crosslinking between the CNTs and amorphous carbon matrix is considered to identify the amount of CNT-matrix covalent bonding that maximizes overall composite properties.

Jensen, Benjamin D.↗

HST-STIS Spectra of Saturn's Rings and Implications for Their Reddening Agent

We obtained HST-STIS spectra of Saturn's main rings in May 2011, using the G230L (and G430L) gratings, with final averaged radial resolution of 160 (and 330) km/pixel. The dataset filled a previous 200-330nm "spectral gap" between Cassini and ground-based spectra. The data provide radial profiles as a function of wavelength, but our most basic product at this point is a set of very low-noise spectra, radially averaged over broad regions of the rings (A, B, C, and Cassini Division). The raw spectra required special processing to remove artifacts due to extended-source grating scatter. We have modeled the spectra using a new particle surface model, which corrects for on-surface shadowing due to the likely very rough ring particle surfaces, and avoids overestimation of intra-mixed "neutral absorber". We correct for non-classical layer effects and finite ring optical depth, and relate our observed reflectivities to the spherical albedos of individual smooth particles. We model these smooth particle albedos using standard Hapke theory for regolith grain mixtures that are either homogeneous and "intramixed" (nonicy absorbers dispersed in water ice regolith grains) or heterogeneous "intimate" mixtures. As candidates for the nonicy contaminants we have considered amorphous carbon, aromatic-rich and aliphatic-rich organic tholins, silicates, hematite and iron metal. For the A and B rings, we find that iron metal (including a new theoretical estimate of the refractive indices of nanometer-sized grains of iron) is not spectrally steep enough in the 200-300nm range, and that aliphatic-rich tholins are either too steep at short wavelengths or too flat at long wavelengths. However, less than 1% by mass of aromatic-rich tholins provides a very good fit across the entire spectral range with no gratuitous "neutral absorber" needed, and a minimum of additional free parameters. The best fits require forward-scattering regolith grains. For the C Ring and Cassini Division, additional absorbers are needed (updated results will be given).

Saturn's Rings↗

Yield and Failure Behavior Investigated for Cross-Linked Phenolic Resins Using Molecular Dynamics

Molecular dynamics simulations were conducted to fundamentally evaluate the yield and failure behavior of cross-linked phenolic resins at temperatures below the glass transition. Yield stress was investigated at various temperatures, strain rates, and degrees of cross-linking. The onset of non-linear behavior in the cross-linked phenolic structures was caused by localized irreversible molecular rearrangements through the rotation of methylene linkers followed by the formation or annihilation of neighboring hydrogen bonds. The yield stress results, with respect to temperature and strain rate, could be fit by existing models used to describe yield behavior of amorphous glasses. The degree of cross-linking only indirectly influences the maximum yield stress through its influence on glass transition temperature (Tg), however there is a strong relationship between the degree of cross-linking and the failure mechanism. Low cross-linked samples were able to separate through void formation, whereas the highly cross-linked structures exhibited bond scission.

Molecular dynamics↗

Sulfur-Bearing Phases Detected by Evolved Gas Analysis of the Rocknest Aeolian Deposit, Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument suite detected SO2, H2S, OCS, and CS2 from approx.450 to 800 C during evolved gas analysis (EGA) of materials from the Rocknest aeolian deposit in Gale Crater, Mars. This was the first detection of evolved sulfur species from a Martian surface sample during in situ EGA. SO2(approx. 3-22 micro-mol) is consistent with the thermal decomposition of Fe sulfates or Ca sulfites, or evolution/desorption from sulfur-bearing amorphous phases. Reactions between reduced sulfur phases such as sulfides and evolved O2 or H2O in the SAM oven are another candidate SO2 source. H2S (approx.41-109 nmol) is consistent with interactions of H2O, H2 and/or HCl with reduced sulfur phases and/or SO2 in the SAM oven. OCS (approx.1-5 nmol) and CS2(approx.0.2-1 nmol) are likely derived from reactions between carbon-bearing compounds and reduced sulfur. Sulfates and sulfites indicate some aqueous interactions, although not necessarily at the Rocknest site; Fe sulfates imply interaction with acid solutions whereas Ca sulfites can form from acidic to near-neutral solutions. Sulfides in the Rocknest materials suggest input from materials originally deposited in a reducing environment or from detrital sulfides from an igneous source. The presence of sulfides also suggests that the materials have not been extensively altered by oxidative aqueous weathering. The possibility of both reduced and oxidized sulfur compounds in the deposit indicates a nonequilibrium assemblage. Understanding the sulfur mineralogy in Rocknest materials, which exhibit chemical similarities to basaltic fines analyzed elsewhere on Mars, can provide insight in to the origin and alteration history of Martian surface materials.

evolved gas analysis↗

Fe-Containing Allophane and Hisingerite Dissolution and Implications for Gale Crater, Mars

The mass-normalized dissolution rates measured in this study demonstrate that hisingerite and Fe-substituted allophane dissolve rapidly, much faster than crystalline phyllosilicates such as nontronite and kaolinite that have similar compositions. In addition, hisingerite dissolves more rapidly than allophane. Future work will focus on measuring dissolution rates at other pH values, so that dissolution rate laws for allophane and hisingerite can be derived. Results will be used to interpret data from Gale Crater. These initial experiments suggest that, if the liquid water present in Gale Crater was highly acidic, it was likely present for only a short time, allowing some amorphous soil-material similar to allophane to persist. Further experiments will enable us to constrain the timescales over which liquid water was present in Gale Crater and provide insight into its pH. This information is essential to assessing the potential habitability of ancient Mars.

Ralston, S. J.↗

Mineralogy of Rock Flour in Glaciated Volcanic Terrains: An Analog for a Cold and Icy Early Mars

Geomorphological and mineralogical data from early Martian surfaces indicate liquid water was present on ancient Mars. The relative surface temperatures, however, remain a subject of debate. Was early Mars warm and wet or cold and icy with punctuated periods of warmth and ice melt? By characterizing the mineralogy and geochemistry of modern icy mafic terrains on Earth, we can search for these characteristics in early Martian terrains to better constrain the early Martian climate. Here, we describe the mineralogy of glacial flour in a modern glaciated volcanic terrain in Oregon, USA. We are particularly interested in secondary phases that form in these environments, and we hypothesize that poorly crystalline phases may preferentially form in these terrains because of the low temperatures and the seasonality of melt water production. A description of the mineralogy of the moraines, the composition of the amorphous materials, and the geochemistry of the glacial melt waters are presented elsewhere. Glacial flour is made up of silt- and clay-sized particles that form from the physical weathering of rock underlying a wet-based glacier as the glacier slides over it. Flour is usually transported from underneath a glacier by melt water streams. The geochemistry of glacial melt water streams has been studied extensively and has been used to infer weathering reactions within glacial systems. However, the mineralogy of these environments, especially on mafic volcanic terrains, is not well studied. Rock flour is a ubiquitous physical weathering product in glaciated terrains and, therefore, affects microbial habitats, stream and lake chemistry, and chemical weathering processes. and by studying the mineralogy of glacial flour, we can better understand geochemical and microbiological processes in subglacial and proglacial terrains.

Rampe, E. B.↗

Single-Step, Solvent-Free, Catalyst-Free Preparation of Holey Carbon Allotropes

Methods for forming holey carbon allotropes and graphene nanomeshes are provided by the various embodiments. The various embodiments may be applicable to a variety of carbon allotropes, such as graphene, graphene oxide, reduced graphene oxide, thermal exfoliated graphene, graphene nanoribbons, graphite, exfoliated graphite, expanded graphite, carbon nanotubes (e.g., single-walled carbon nanotubes, double-walled carbon nanotubes, few-walled carbon nanotubes, multi-walled carbon nanotubes, etc.), carbon nanofibers, carbon fibers, carbon black, amorphous carbon, fullerenes, etc. The methods may produce holey carbon allotropes without the use of solvents, catalysts, flammable gas, additional chemical agents, or electrolysis to produce the pores (e.g., holes, etc.) in the carbon allotropes. In an embodiment, a carbon allotrope may be heated at a working window temperature for a working period of time to create holes in the carbon allotrope.

Lin, Yi↗

A New Method of Absorption-Phase Nanotomography for 3D Observation of Mineral-Organic-Water Textiles and its Application to Pristine Carbonaceous Chondrites

Pristine carbonaceous chondrites contain fine-grained matrix, which is composed largely of amorphous silicates, sub-micron silicate and sulfide crystals, and organic materials. They are regarded as primitive dust in the early Solar System that have suffered minimal alteration in their parent bodies. The matrix generally has different lithologies; some of them are unaltered but some are more or less aqueously altered. Their textures have been examined in 2D usually by FE-SEM/EDS, TEM/EDS, nano-SIMS and micro-XRD. Observation of their complex fine textures, such as spatial relation between different lithologies in 3D, is important for understanding aggregation and alteration processes. Synchrotron radiation (SR)-based X-ray tomography reveals 3D structures nondestructively with high spatial resolution of approximately greater than 100 nm. We have developed a new technique using absorption contrasts called "dual-energy tomography" (DET) to obtain 3D distribution of minerals at SPring-8, SR facility in Japan, and applied successfully to Itokawa particles. Phase and absorption contrast images can be simultaneously obtained in 3D by using "scanning-imaging x-ray microscopy" (SIXM) at SPring-8, which can discriminate between void, water and organic materials. We applied this technique combined with FIB micro-sampling to carbonaceous chondrites to search for primitive liquid water. In this study, we combined the DET and SIXM to obtain three dimensional submicron-scale association between minerals, organic materials and water and applied this to pristine carbonaceous chondrites.

Tsuchiyama, A.↗

Constraints on the Mineralogy of Gale Crater Mudstones from MSL SAM Evolved Water

The Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments on the Mars Science Laboratory (MSL) have analysed more than 150 micron fines from 14 sites at Gale Crater. Here we focus on the mudstone samples. Two were drilled from sites John Klein (JK) and Cumberland (CB) in the Sheepbed mudstone. Six were drilled from Murray Formation mudstone: Confidence Hills (CH), Mojave (MJ), Telegraph Peak (TP), Buckskin (BK), Oudam (OU), Marimba (MB). SAM's evolved gas analysis mass spectrometry (EGA-MS) detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases, including organic fragments. The identity and evolution temperature of evolved gases can support CheMin mineral detection and place constraints on trace volatile-bearing phases or phases difficult to characterize with X-ray diffraction (e.g., amorphous phases). Here we will focus on SAM H2O data and comparisons to SAM-like analyses of key reference materials.

McAdam, A. C.↗

Refractory Organics in Comet 67P Churyumov-Gerasimenko: Additional Evidence for Large-scale Mixing in the Primitive Solar Nebula?

The COSIMA instrument onboard the Rosetta spacecraft collected and analyzed samples of individual particles from the coma of Comet67P/ Churyumov-Gerasimenko. Initial results of the analysis of several particles have been presented elsewhere while analyses of the organic component of the dust particles has been shown to compare favor ably to laboratory spectra of IOM extracted from the Orguil and Murchison meteorites. Here we will compare the spectra of the same two particles to laboratory spectra of organic grain coatings produced via Surface Mediated Reactions of CO, H2 and N2 on amorphous iron silicate grains.

Refractory Organics↗

Infrared Spectra and Band Strengths of CH3SH, an Interstellar Molecule

Three solid phases of CH3SH (methanethiol or methyl mercaptan) have been prepared and their mid-infrared spectra recorded at 10-110 degrees Kelvin, with an emphasis on the 17-100 degrees Kelvin region. Refractive indices have been measured at two temperatures and used to estimate ice densities and infrared band strengths. Vapor pressures for the two crystalline phases of CH3SH at 110 degrees Kelvin are estimated. The behavior of amorphous CH3SH on warming is presented and discussed in terms of Ostwald's step rule. Comparisons to CH3OH under similar conditions are made, and some inconsistencies and ambiguities in the CH3SH literature are examined and corrected.

Astrochemistry↗

Laboratory Investigations into the Spectra and Origin of Propylene Oxide: A Chiral Interstellar Molecule

Propylene oxide was recently identified in the interstellar medium, but few laboratory results are available for this molecule to guide current and future investigations. To address this situation, here we report infrared spectra, absorption coefficients, and band strengths of solid propylene oxide along with the first measurement of its refractive index and a calculation of its density, all for the amorphous solid form of the compound. We present the first experimental results showing a low-temperature formation pathway for propylene oxide near 10 K in interstellar ice analogs. Connections are drawn between our new results and the interstellar molecules propanal and acetone, and predictions are made about several as yet unobserved vinyl alcohols and methylketene. Comparisons are given to earlier laboratory work and a few applications to interstellar and solar system astrochemistry are described.

molecular processes↗

Great New Insights from Failed Experiments, Unanticipated Results and Embracing Controversial Observations

Experimental data and observations, whether telescopic or analytical, are never wrong, though data derived from such sources can be misinterpreted or applied inappropriately to derive conclusions that are incorrect. Given that nature always behaves according to the laws of physics and chemistry, rather than according to currently popular models and theories, experimental results should always be considered correct even when the results are far from those that one might initially expect. We discuss a number of cases where the results of experiments, even one carried out as a simple calibration measure, produced wildly different results that generally required many years of effort or contemplation to understand. On the positive side, exploration of the circumstances that produced the errant results often led to new and interesting insights concerning processes that might occur in natural environments and that were well worth the effort involved. Specifically, we show how an experiment that "failed" due to a broken conductor led to experiments that made the first refractory oxide solids containing mass independently fractionated oxygen isotopes and to 1998 predictions of the oxygen isotopic composition of the sun that were confirmed by the analysis of Genesis samples in 2011. We describe a calibration experiment that unexpectedly produced single magnetic domain iron particles. We discuss how tracking down a persistent source of "contamination" in experiments intended to produce amorphous iron and magnesium silicate smokes led to a series of studies on the synthesis of carbonaceous grain coatings that turn out to be very efficient Fischer-Tropsch catalysts and have great potential for trapping the planetary noble gases found in meteorites. We describe how models predicting the instability of silicate grains in circumstellar environments spurred new measurements of the vapor pressure of SiO partially based on previous experiments showing unexpected but systematic non-equilibrium behavior instead of the anticipated equilibrium products resembling meteoritic minerals. We trace the process that led from observations of the presence of crystalline minerals detected in the comae of some comets to the 1999 prediction of large-scale circulation of materials from the hot, innermost regions of the solar nebula out to the cold dark nebular environments where comets form. This large-scale circulation was ultimately confirmed by analyses of highly refractory Stardust samples collected from the Kuiper Belt Comet Wild 2. Finally we discuss a modern and still unresolved conflict between the assumptions built into three well known processes: the CO Self Shielding Model for mass independent isotopic fractionation of oxygen in solar system solids, rapid and thorough mixing within the solar nebula, and the efficient conversion of CO into organic coatings and volatiles on the surfaces of nebular grains via Fischer-Tropsch-type processes.

controversial↗

Jet Fuel Thermal Stability Investigations using Ellipsometry

Ellipsometry is an optical technique used to measure the thickness of thin films. This technique was used to measure the thickness of deposits created by heated jet fuel, specifically Sasol IPK on stainless steel tubes. A new amorphous model was used to iteratively determine the film thickness. This method was found to be repeatable, and the thickness of deposit increased with increasing temperature and increasing concentration of naphthalene.

aviation fuel↗